Dihydronordicyclopentadienyl-substituted formals



l is represented by the'structure Patented June 29, 1948 rss PATENT :OFiF lCE DIHYDRONORDIGYCLOPENTADIENYL- SUBSTITUTEDiFORMALS l' Herman A. Bruson, .RydaLtP-a assignor to .The Resinous IProducts & Chemical "Company, "Philadelphia,'Pa., a corporation of Delaware No Drawing. Original application :March 9,

1944,: Serial No.:.52 5,757. ;.Dividedsandthis v applicationJuly 13,1946, Serial No. 683,412

This invention relates to formals of alcoholscontaining a, dihydronordicyclopentadienyl group and to a method for the preparation of these formals from formaldehyde .and said alcohols in the presence of an acidic condensing agent.

'The"formals' of this invention are of the general formula twhereiniz :isxa monovalent organic 'leSidHQJWhiOh :contains a ndihydronordicyclopentadienyl group, iwGmHn, and :which: is, joined to: the indicated lmethylenergroup through etherrzoxygen. i

:L'J -hentruc-turewf:the:Edihydronordicyclopentadi- ;enyl ;gro upxmay berepresented!v'bytthe;following forrnulae, th'e first being thezmcre, probable,

on on: "CH/ -'oH- 01; fl 30H on k com C gdihydronordicyclopentadienyl group 'CioHi3-- cy lo entadien itached to its addedsubstituem group,,a, at a sec- )ondary-carbon atom flanked by a methylene group group which forms with. "The'formals of. greatest interest have the genlyzed, addition-rearrangement reactions from di- "Itis monoyalent and'is atand aitertiary carbon atom in an endoeth'ylene cyclopentan'o group carrying the propenylene a cyclopenteno group thereeral'formula wherein C1oH-1s isthedihydronordicyclopentadienyl group, Arislanalkylene group of at least two carbon atoms, and ii. is zero oran integer. A may also represent an alkylene group having a halogen. on an ether 1 groupas a substituent.

EThB formals of this invention are obtained by condensing formaldehyde in the presence of an acidic condensing agent with an alcohol containing the dihyd-ronordicyclopentadienyl system.

-Such .alcohols are new compounds resulting from. the addition rearrangement reaction of -di cyclopentadiene with wateroig .polyh'ydricalcohols in the presence of sulfuric acid or other acidic condensing agents,- as described in my patent applications Serial-Nos.' 476,640 and 476,645, filed February 20, ,.1943, and now wissuedr as United States Patents. Nos, 2,394,582 and 2,385,788, respectively. As ,polyhydrioalcoholsthere: may be [used ethylene glycol, propylene glycol, trimethylene .glycolwthewariqushutylene glycols, and

glycols having larger. alkylene groups, .polyalkylene ,glycolsn such as .diethylene glycol, triethylene glywherein Cal-I4 is a propenylene group which in .45 selvcs'with'more than twohydroxylgrou s,

Typical dihydronordicyclopenta-dienyl-containing alcohols which are useful for the preparation of formals of this invention are, by way of example, the following:

4 of 52 grams. The desired formal distilled over between 183 and 203 C. at 1.5-3 mm. as a colorless oil- The yield was 215 grams. Upon redistillation it boiled at 180 C. at 2 mm.

The condensation of formaldehyde with any of these alcohols containin a dihydronordicyclopentadienyl group takes place readily at 50- 150 C. or somewhat higher by heating a mixture of formaldehyde with the alcohol in the presence of an acidic condensing agent. Thereactant's are preferably mixed in a ratio of about one mol of formaldehyde to two mols of the alcohol, but excess of either reactant is permissible. Typical of the acidic condensing agents which .may be used are phosphoric acid, sulfuric acid,

hydrochloric acid, dihydroxyfluoboric acid, acidic siliceous clays, benzene sulfonic acid, zinc chloride, phosphotungstic acid, and the like, The quantity of acidic condensing agents used is small, an amount from 0.5% to 5% of the weight of the reactants being. usually sufncient for the purpose.

Water is evolved and is advantageously removed by utilizing an organic solvent, such as benzene or toluene, to help distill off the water in an azeotropic mixture as fast'as it is formed. -In place of benzeneth'ere may be used otherinert solvents, including hydrocarbons, such as toluene and xylene, ethers such as propyl r 'butyl ethers, chlorinated solvents such as .di-chloroor tetrachloro-ethane, and the like.

After the reaction is complete, the crude product is neutralized with alkali and the product isolated by vacuum distillation, by steam-vacuum distillation, or simply by stripping oif the solvent and low-boiling impurities with subsequent clarification or bleaching of the residual high-boiling product.

The formals obtained are high-boiling oils or low-melting solids yielding viscous, oily liquids of particular value for the preparation of autoxidizablecoatings/ The following examples illustrate this invention, it being understood that the paraformaldehyde can be'replaced with trioxymethylene or aqueous formaldehyde.

A mixture of 300 grams of 'hydroxydih'ydronordicyclopentadiene, 30 grams of paraformaldehyde, 200 grams of benzene, and 10 grams of Formula From Dicyclopentadiene and l CmHm-OH Water. 2 O10H;3OCH2CH2OH Ethylene glycol. 3 C uH sOCHzOHr-O-CHzCHzOH Dlethylene glycol. 4 C1oHmOCHzOHzO-CH2CH2OCH2CH2OH Tnethyleneglycol. 5 C1uH1s(OCHzCH2),.OH, where n is a whole number, particularly two to nine Corresponding polyethylene glycols. 6 OH13O-GH2CH2OH2OH Tnmethylene glycol. 7 OmH -OCH CH(OH )OH Propaylene glycol. 8 C16H13-OCH(OH3) (CH3) OHOH a 2, 3- utylene glycol. 9 C10H13OCHzCH(CH3)O (GH;) OHCHZOH Dipropylene glycol. 10 C1oH13OC H2 OHOH OH2 OCH3 GlyceryI-monomethyl ether. 11 C QH sO'CH2-CHOHCH CI l. Glyceryl monochlorohydnn. l2 C H1 O0H2CH0HCHzOC5115..- Glyceryl monophenyl ether. 13 GmHn-O-GH2OHOHCH2OC10H;3 GlYCGIOl. 14 CwH13-0-C H2OHOHCH20a1lyl Glyceryl-monoallyl ether. 15 Oi0H130CH2-(OH2)4CH20H Hexamethylene glycol. 16 C oH1 O-CH (CH2) OH OH Decamethylene glycol.

The hydroxydihydronordicyclopentadienyl for- ,mal thus obtained polymerizes to a colorless, very as the unpolymerized formal dries by autoxidation upon exposure to the air, alone or with siccatives', to a colorless varnish-like film. It can also be blended with drying oils such as linseed oi1-to yield high quality varnishes and baking enamels.

, Erample 2 Ol0Hl3-0-OH2CH2-O CH2 ClnH1r-O-CH2CH2-O A mixture consisting of v291 gramsof beta-hydroxyethoxydihydronordicyclopentadiene,

HOCH2CH2-O-C10H13 together with 200 grams of benzene, 30 grams of paraformaldehyde, and 10 grams of phosphoric acid was stirred and boiled under a reflux condenser attached to a water trap for three .hours at 85 -93 C. until 20 grams of water had collected in the trap. The product was washed with dilute sodium hydroxide solution to remove the catalyst, and the washed product evaporated to dryness to recover the solvent, The residual oil was distilled in vacuo.

The di- (dihydronordicyclopentadienyloxyethyl) formal distilled over at 235-245 C./1.5 mm. as an almost colorless oil. The yield was 212 grams. About 57 grams of unchanged ether alcohol was recovered.

Example 3 A mixture consisting of 300 grams of hydroxydihydronordicyclopentadiene, 35 grams of paraformaldehyde, 200 grams of benzene, and 30 grams of acid Tonsil clay (trademark for a brand of hydrated magnesium aluminum silicate) was rapidly stirred and boiled under a reflux condenser attached to a water trap. After about two hours heating at 82-95 C., 21 grams of water had collected in the trap. The product was filtered hot by suction and the benzene distilled off from the clear filtrate, Theresidual oil upon distillation in vacuo yielded 253 grams of di- (dihydronordicyclopentadienyl) formal, boiling between 180 and 200 C. at 2 mm., identical with that of Example 1.

1 mixture consisting ;of 113' :grams of :betaliydroxyethoxw ethoxy dihydronordicyclopentadien e, 7:15.. grams of :paraformaldehyde, 100 :grams of :benzene, [and 10 grams of acid Tonsil4clay was stirred and boiled forx80 minutes under a reflux.condensereattached to a water trap, .until seventgramsof water'had come over. The product was filtered and distilled. The 1di(dihydronordi cyclopentadienyloxyethoxyethyl) formal distilled as an almost-colorless oil at 285 C./2 mm. The

yield was 85 grams.

E m e 5 A mixture consisting of 208 Jgrams'of gammahydroxypro pyloxydihydronordicyclop e rrt a'd i e ne,

C1oH13O--CH2CH2CH2OH, 24 grams of. paraformaldehyde, 150 grams of benzene, and grams of acid Tonsil clay was boiled under a reflux condenser until 12 cc. of water had collected in a trap attachedthereto. This required two hours. The reaction mixture wasfiltered to remove the iclay,;andthe filtrate .evaporatedto .dry-ness. 1 The residual oil was distilled-in yacuo at $2.5 1mm. pressure. 'The fraction iboiling at 2602270 "(3.12.5 1mm. was the desired uformal.

The-yieldwas165 gram-s. It is a :COIOIflGSSJOil.

" Example 6 o CH3O-CH2-$HCH2OC10H13 distilled over at 267-274 C./2.5 mm. as a colorless oil.

In a similar manner the following formals are obtained as thick oils from the corresponding alcohols in the list given above.

clone- 0-cHzs-o.H-oHr-.om1 1 UmEn-O-GHr-(QB-r)k-GHf-O' CioH1a-0-CH2(CH2)r-CH2-O CioH1a-OCH:(GH2)s'-CHa--O CioH1x-OGH2(CH2)a-CH2O The above compounds, when blown with air at 0., go over to extremely viscous oils and resins which absorb oxygen from the air. They have the unique property of drying in air by absorption of oxygen, behaving in this respect like the natural drying oils, such as linseed oil or tung oil. They also polymerize to viscous oils useful as varnishes either alone or when blended or co-polymerized with drying oils, alkyd resins, or other resins. They may be mixed with vinyl and acrylic compounds which are then polymerized. They may be used not only for paints, varnishes, and lacquers but also as bonding materials for cork and fibres, as for the preparation of linoleum, molding compositions, laminated fabrics, and the like,

The present application is a division of application Serial No. 525,757, filed March 9, 1944, which issued on February 18, 1947 as United States Patent No. 2,416,250. It is directed to polyether formals of the formula C1nH1a(0A)n- /CH2 C1oH1a(OA)nO wherein n is an integer from one to nine, inclusive.

Iclaim:

1. .As new compounds, structure formals having the wherein A is an alkylene group having two to ten carbon atoms, n is an integer from one to nine, inclusive, and C1oH13-- is the monovalent dihydronordicyclopentadienyl radical formed from dicyclopentadiene during acid-catalyzed, addi- 1 Hon-rearrangement reactions of hydroxylated compounds therewith and which is characterized by attachment to its substituent group at a secondary carbon atom flanked by a methylene group and by a tertiary carbon atom.

2. As new compounds, formals having the structure wherein n is an integer from one to nine, inclusive, and C1oH13 is the monovalent dihydronordicyclopentadienyl radical formed from dicyclopentadiene during acid-catalyzed, addition-rearrangement reactions of hydroxylated compounds therewith and which is characterized by attachment to its substituent group at a secondary carbon atom flanked by a methylene group and by a tertiary carbon atom. v

3. As a new compound, the formal or hydroxyethoxydihydronordicyclopentadiene,

010E130 CHzCHzO 010E130 CHECHiO wherein CH13- is the monovalent dihydronordicyclopentadienyl radical formed from dicyclopentadiene during acid-catalyzed, addition-rear- "8 rangement reactions of hydroxylated compounds therewith and which is characterized by attachment to its substituent group at a secondary carbon atom flanked by a methylene group and by a tertiary carbon atom.

4; As a new compound, the formal of hydroxyethoxyethoxydihydronordicyclopentadiene,

010E CHaC H2O CH2CH2O I OH:

CmHnO OH2CH2O CHzCHaO wherein C10H13-- is the monovalent dihydronordicyclopentadienyl radical formed from dicyclopentadiene during acid-catalyzed, addition-rearrangement'reactions of hydroxylated compounds wherein C10H13 is the monovalent dihydronordicyclopentadienyl radical formed from dicyclopentadiene during acid-catalyzed, addition-rearrangement reactions of hydroxylated compounds therewith and which is characterized by attachment to its substituent group at a secondary carbon atom flanked by a methylene group and by a tertiary carbon atom.

HERMAN A. BRUSON.

Certificate of Correction Patent No. 2,444,090. June 29, 1948. HERMAN A. BRUSON It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Column 3, line 23, for 150 0. read 150 0.; column 5, Example 6, line 47, for the right-hand portion of the formula reading O H read O H column 5, line 71, for that portion of the formula reading (CH-O read O'HO; column 6, line 19, for O G read 0 51 and that the said Letters Patent should be read=with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 14th day of September, A. D. 1948.

THOMAS F. MURPHY,

Assistant Gammisst'oner of Patents. 

